JP5998727B2 - Foam laminated sheet - Google Patents

Description

  The present invention relates to a laminated sheet and a foam laminated sheet. The foamed laminated sheet has a foamed resin layer and is useful as foamed wallpaper, various decorative materials, and the like. The laminated sheet means a state before foaming of the foamed laminated sheet (so-called unfoamed raw fabric) or a sheet useful as various decorative materials in a state where no foamed resin layer is provided.

  In recent years, with the improvement of energy conservation orientation, there is a demand for highly airtight houses with improved energy efficiency. For example, it is known that in a house using the outer heat insulation method, airtightness is improved and air conditioning efficiency in summer and winter is improved.

  On the other hand, as the air tightness of the house improves, the air permeability decreases, so the problem of sick house caused by organic gas such as formaldehyde generated from the house members, and the volatile organic compounds (VOC) such as pet odor and living odor swell. There is a problem that it becomes easy.

  In recent years, as a countermeasure to these problems, there has been an increasing need for interior materials for buildings having a deodorizing function for adsorbing and deodorizing VOCs. Examples of building interior materials having a deodorizing function include wall materials, ceiling materials, floor materials, etc., but they can be used as wall materials having the largest area as interior materials for VOC adsorption and deodorization. Various wallpapers that are considered effective and have a deodorizing function have been proposed.

  For example, Patent Document 1 discloses “a wallpaper having a coating layer containing a material that adsorbs a volatile organic compound on the surface of a base sheet” (Claim 1). Thereby, it is said that the density | concentration of the pollutant contained in indoor air can be reduced efficiently.

  Here, as materials (adsorbents) that adsorb VOCs, there are inorganic adsorbents made of inorganic materials such as zeolite and silica gel, and organic-inorganic composite adsorbents in which organic functional groups such as amino groups are bonded to inorganic materials. It is known that the organic / inorganic composite adsorbent exhibits a high deodorizing function.

  However, the conventional wallpaper as in Patent Document 1 has the following problems. In other words, in conventional wallpaper and the like, the coating layer containing the adsorbent is located on the surface of the wallpaper. Therefore, particularly when an organic-inorganic composite adsorbent is used as the adsorbent, contaminants and chemicals adhere to the wallpaper surface. Therefore, there is a problem that the wallpaper surface is colored or discolored. Specifically, coloring due to adhesion of contaminants and chemicals to the organic / inorganic composite adsorbent, discoloration due to reaction with the organic / inorganic composite adsorbent after the attachment, etc., resulting in insufficient stain resistance and chemical resistance. It is said that.

  Moreover, when more adsorbents are blended in order to obtain high deodorant performance, the coating layer becomes thick and the adsorbent is buried in the layers, and on the contrary, the deodorizing effect may not be sufficiently exhibited. Further, since the drying property is deteriorated by increasing the thickness, productivity problems such as blocking may occur.

  Accordingly, a laminated sheet and a foamed laminated sheet in which a layer containing at least an organic-inorganic composite adsorbent is formed on a substrate, exhibiting a sufficient deodorizing effect and improving stain resistance and chemical resistance. In addition, development of highly productive laminated sheets and foamed laminated sheets is desired.

JP-A-10-310984

  The present invention is a laminated sheet and a foamed laminated sheet in which a layer containing at least an organic-inorganic composite adsorbent is formed on a substrate, and exhibits a sufficient deodorizing effect and has stain resistance and chemical resistance. An object is to provide a laminated sheet and a foamed laminated sheet which are improved and have high productivity.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by a laminated sheet and a foamed laminated sheet having a specific layer structure, and have completed the present invention.

That is, the present invention relates to a foamed laminated sheet below.
1. A foam laminated sheet in which at least two layers of a lower coating layer and an upper coating layer are formed on a substrate,
(1) The lower coating layer contains an organic-inorganic composite adsorbent that adsorbs a resin component and a volatile compound, the resin component contains an acrylic resin,
(2) The upper coating layer contains a resin component, the resin component contains an acrylic resin,
(3) the total thickness of said lower cover layer and the upper coating layer Ri der less 15 [mu] m,
(4) having a foamed resin layer between the base material and the lower coating layer;
(5) Embossed from the top surface layer.
A foamed laminated sheet characterized by that.
2 . Item 2. The foamed laminated sheet according to Item 1 , wherein the foamed resin layer is an olefin resin layer.
3 . The upper covering layer contains an inorganic adsorbent for adsorbing the volatilization compounds, foamed laminate sheet according to 1 or 2.
4 . Item 4. The foamed laminated sheet according to any one of Items 1 to 3 , wherein a total thickness of the lower coating layer and the upper coating layer is 10 µm or less.
5 . Item 5. The foamed laminated sheet according to any one of Items 1 to 4, wherein the foamed resin layer has a non-foamed resin layer on one side or both sides.
6 . The foamed laminated sheet according to any one of Items 1 to 5 , wherein the lower coating layer contains an organic-inorganic composite adsorbent that adsorbs 5 to 80 parts by mass of the volatile compound with respect to 100 parts by mass of a resin component. .
7 . The foamed laminated sheet according to any one of Items 3 to 6 , wherein the upper coating layer contains an inorganic adsorbent that adsorbs 5 to 120 parts by mass of the volatile compound with respect to 100 parts by mass of the resin component.
8 . Item 8. The foamed laminated sheet according to any one of Items 1 to 7 , wherein the foamed resin layer is resin-crosslinked by electron beam irradiation.

Hereinafter, the laminated sheet and the foamed laminated sheet of the present invention will be described in detail.
≪Laminated sheet≫
In the laminated sheet of the present invention, at least two layers of a lower coating layer and an upper coating layer are formed on a substrate,
(1) The lower coating layer contains an organic-inorganic composite adsorbent that adsorbs a resin component and a volatile compound (hereinafter abbreviated as “organic-inorganic composite adsorbent”),
(2) The total thickness of the lower coating layer and the upper coating layer is 15 μm or less.
It is characterized by that.

  The laminated sheet of the present invention having the above characteristics is formed by forming at least two layers of a lower coating layer and an upper coating layer on a substrate, and containing a resin component and an organic-inorganic composite adsorbent in the lower coating layer. Stain resistance and chemical resistance have been improved. In addition, since the total thickness of the lower coating layer and the upper coating layer is 15 μm or less, even if the lower coating layer containing the organic-inorganic composite adsorbent is not located on the outermost surface, it exhibits an excellent deodorizing function. In addition, problems such as blocking are avoided due to excellent drying properties, and productivity is high. These effects are also the same in the foamed laminated sheet obtained by foaming the foaming agent-containing resin layer.

Not limited as the substrate base material, a known fibrous sheet (backing paper), a synthetic resin sheet, etc. can be utilized.

  Specifically, wallpaper general paper (pulp-based sheet sized with a known sizing agent); flame-retardant paper (pulp-based sheet treated with a flame retardant such as guanidine sulfamate or guanidine phosphate) ); Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper; synthetic fiber mixed paper.

Although the basis weight of the substrate is not critical, preferably about 50 to 300 g / m ^2, more preferably about 50~120 g / m ^2.

Lower coating layer and upper coating layer In the laminated sheet of the present invention, at least two layers of a lower coating layer and an upper coating layer are formed on a substrate. The lower coating layer contains a resin component and an organic / inorganic composite adsorbent, and the total thickness of the lower coating layer and the upper coating layer is 15 μm or less.

  The resin component constituting the lower coating layer is not limited, but acrylic resin, urethane resin, polyester resin, styrene resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, etc. are preferable. . By adopting these resin components, effects such as contamination resistance and adhesion can be further enhanced.

  Examples of the organic / inorganic composite adsorbent contained in the lower coating layer include, for example, organic / inorganic materials in which an inorganic compound carries an organic compound such as hydroxyl group, amines, ureas, amides, imides, hydrazides, azoles, azines A composite adsorbent may be mentioned. Examples of the inorganic material that can be used as the carrier include silicon dioxide, activated carbon, sepiolite, and mica from the viewpoint of heat resistance. Specifically, those in which an amine having a primary amino group is supported on the inorganic material are preferable. Such an organic-inorganic composite adsorbent is particularly effective for adsorption and deodorization of aldehydes such as formaldehyde and acetaldehyde.

  The adsorption mechanism of the volatile compound of the organic-inorganic composite adsorbent may be either chemical adsorption or physical adsorption. Here, “chemical adsorption” is to adsorb volatile compounds by chemical bonding, and “physical adsorption” is to adsorb volatile compounds by van der Waals force.

The average particle size of the organic / inorganic composite adsorbent is not limited, but is preferably 1 to 12 μm, and more preferably 2 to 5 μm. Here, the average particle diameter in the present specification is a value measured by a laser diffraction scattering method. Although the specific surface area of the organic-inorganic composite adsorbent not critical, preferably ^{400~900m 2 / g, 500~900m 2 /} g is more preferable. Here, the specific surface area in this specification is a value measured by the BET method. The content of the organic-inorganic composite adsorbent is preferably 5 to 140 parts by mass with respect to 100 parts by mass of the resin component contained in the lower coating layer from the viewpoint of obtaining sufficient deodorization performance, and the durability of the lower coating layer From the standpoint of retention and production stability of the organic / inorganic composite adsorbent, 5 to 80 parts by mass is more preferable, and 20 to 60 parts by mass is most preferable.

The thickness of the lower coating layer is preferably 0.5 to 10 μm, and more preferably 0.5 to 5 μm. The measured value of the thickness of the lower coating layer is a value measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Generally, a thin layer close to the nano order is measured by a TEM, and a micro order layer is Although measured by SEM, the numerical value is the same regardless of which is measured (the measurement method of the thickness of the upper coating layer described later is also the same). In terms of coating amount, 0.5 to 10 g / m ² is preferable, and 0.5 to 5 g / m ² is more preferable. In relation to the average particle diameter of the organic / inorganic composite adsorbent, it is preferable that the thickness of the lower coating layer <the average particle diameter. Thus, since the average particle diameter is larger, the adsorbent part rises from the coating film, and the distance from the surface becomes closer, so that the deodorizing function can be enhanced.

  The lower coating layer can be formed, for example, by applying an ink composition containing an organic-inorganic composite adsorbent based on an emulsion ink in which the resin component is dispersed. In addition, the lower coating layer can be blended with known surfactants such as antifoaming agents and leveling agents, viscosity modifiers, extenders and other additives within a range that does not affect the effects of the present invention. . In the present invention, the content of the organic-inorganic composite adsorbent in the solid content (organic-inorganic composite adsorbent, resin component and the additive) constituting the lower coating layer is sufficient to obtain sufficient deodorizing performance, From the viewpoint of imparting suitable ink suitability to the ink composition, it is preferably in the range of 4.0 to 55% by mass. Furthermore, it is more preferable that the range is 4.0 or more and less than 45.0% by mass, and it is possible to prepare the ink composition so as to be in such a range, the stability of the ink composition and the durability after the coating film is formed (adsorbent). Is preferable from the viewpoint of sufficiently obtaining the retention property.

  The resin component constituting the upper coating layer is not limited, but acrylic resin, urethane resin, polyester resin, styrene resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, etc. are preferable. . By adopting these resin components, effects such as contamination resistance and adhesion can be further enhanced.

  Since the upper coating layer does not actively contain the organic / inorganic composite adsorbent, in the present invention, it is possible to ensure contamination resistance and chemical resistance. Since the upper coating layer is located on the outermost surface, an adsorbent other than the organic-inorganic composite adsorbent (in particular, an inorganic adsorbent that adsorbs a volatile compound (hereinafter abbreviated as “inorganic adsorbent”)), By adding various additives such as a matting agent, various functions can be imparted to the laminated sheet. In particular, when an inorganic adsorbent is blended in the upper coating layer, various VOCs (aldehydes, sulfur compounds, acidic compounds, basic compounds, etc.) are adsorbed and extinguished in combination with the organic / inorganic composite adsorbent in the lower coating layer. Since it can smell, it is preferable.

  Examples of the inorganic adsorbent that can be blended in the upper coating layer include zeolite, silica gel (silicon dioxide), aluminum phosphate, hydroxyapatite, activated carbon, mica and the like. Such an inorganic adsorbent is particularly effective for adsorption and deodorization of VOCs such as acetic acid and ammonia. In addition, these inorganic adsorbents are less likely to be colored or discolored by pollutants or chemicals compared to organic-inorganic composite adsorbents, and do not cause deterioration of the stain resistance and chemical resistance of laminated sheets and foamed laminated sheets. .

  The adsorption mechanism of the volatile compound of the inorganic adsorbent may be either chemical adsorption or physical adsorption, similar to the organic-inorganic composite adsorbent.

The average particle size of the inorganic adsorbent is not limited, but is preferably 1 to 7 μm, and more preferably 2 to 5 μm. Although the specific surface area of the inorganic adsorbent is not critical, preferably ^{100~800m 2 / g, 200~800m 2 /} g is more preferable. The content of the inorganic adsorbent is 5 to 140 parts by mass with respect to 100 parts by mass of the resin component contained in the upper coating layer from the viewpoint of obtaining sufficient deodorizing performance and the point of giving suitable ink suitability to the ink composition described later. From the viewpoint of sufficiently obtaining the stability of the ink composition and durability after forming a coating film (such as adsorbent retention), 5 to 120 parts by mass is more preferable, and 20 to 120 parts by mass is even more preferable. .

  As other additives that can be blended in the upper coating layer, for example, within a range that does not affect the effect of the present invention, a weather resistance improver, an infrared absorber, an antistatic agent, an adhesion improver, an antifoaming agent, Examples include fillers (matting agents that enhance surface contamination resistance, slipperiness, matting properties, etc.), colorants, preservatives, leveling agents, dispersants, anti-settling agents, thickeners, and the like.

The thickness of the upper coating layer is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm. In terms of coating weight is preferably ^{0.5~5g / m 2, 0.5~4g / m} 2 is more preferable. In relation to the average particle diameter of the inorganic adsorbent, it is preferable that the thickness of the upper coating layer <the average particle diameter. Thus, since the average particle diameter is larger, the adsorbent part rises from the coating film, and the distance from the surface becomes closer, so that the deodorizing function can be enhanced.

  The upper coating layer can be formed, for example, by applying an ink composition based on an emulsion ink in which the resin component is dispersed and blended with an additive such as an inorganic adsorbent.

  In the present invention, the total thickness of the lower coating layer and the upper coating layer is 15 μm or less, preferably 10 μm or less, and more preferably 5 μm or less. When the total thickness is 15 μm or less, a sufficient deodorizing effect is exhibited, and problems such as blocking are avoided due to excellent drying properties, resulting in high productivity. Further, it is difficult to cause resin cracking that easily occurs when the resin of the coating layer is hard by post-processing, and it is possible to prevent a decrease in contamination due to the resin crack. In addition, when embossing is performed from the surface of the coating layer, the coating layer easily follows changes in the ground during pressurization, so that uneven molding is less likely to occur. Moreover, since gloss is easy to adjust, it becomes easy to provide the design property which was excellent in the lamination sheet. These effects are particularly remarkable when the laminated sheet is a foam laminated sheet. In addition, after laminating | stacking a lower coating layer and an upper coating layer, although based also on the average particle diameter of the adsorption agent mix | blended with each layer, the interface of each layer is not necessarily clear.

Resin layer The laminated sheet of the present invention may have a resin layer between the substrate and the lower coating layer.

  As the resin component contained in the resin layer, vinyl chloride resin, olefin resin, and the like conventionally used for wall covering materials can be widely used, but olefin resin is preferable from the viewpoint of enhancing durability of the laminated sheet. Specifically, it is preferable to contain an ethylene-based resin.

  Examples of the ethylene-based resin include not only polyethylene (PE) but also an ethylene copolymer having monomers other than ethylene and components (hereinafter abbreviated as “ethylene copolymer”).

  As the polyethylene, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and the like can be widely used.

  Ethylene copolymers are suitable for extrusion film formation in terms of melting point and MFR. Examples of the ethylene copolymer include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer ( EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylic acid copolymer (EMAA), ethylene-α olefin copolymer, and the like. These ethylene copolymers can be used alone or in admixture of two or more. Among these ethylene copolymers, ethylene-vinyl acetate copolymer and ethylene-methyl methacrylate copolymer are particularly preferred. When any one of these is used in combination with one or more other resins, ethylene -The content of vinyl acetate copolymer and ethylene-methyl methacrylate copolymer is preferably 70% by weight or more, and more preferably 80% by weight or more.

  Moreover, as for content of monomers other than ethylene, 5-25 weight% is preferable and, as for ethylene copolymer, 9-20 weight% is more preferable. By adopting such a copolymerization ratio, the extrusion film forming property is further enhanced. As a specific example, the ethylene-vinyl acetate copolymer has a vinyl acetate copolymerization ratio (VA amount) of preferably 9 to 25% by weight, more preferably 9 to 20% by weight. The ethylene-methyl methacrylate copolymer has a methyl methacrylate copolymerization ratio (MMA amount) of preferably 5 to 25% by weight, more preferably 5 to 15% by weight. Further, the ethylene-methacrylic acid copolymer is preferably 2 to 15% by mass, more preferably 5 to 11% by mass as the copolymerization ratio (MAA amount) of acrylic acid.

  In the present invention, the resin component contained in the resin layer preferably has an MFR (melt flow rate) measured at 190 ° C. and a load of 21.18 N described in JIS K 6922 of 10 to 25 g / 10 min. When the MFR is within the above range, the temperature rise when forming the resin layer by extrusion film formation is small, and the film can be formed in a non-foamed state. The printing process can be performed, and there are few missing patterns. If the MFR is too large, the resin is too soft and the resulting resin layer may have insufficient scratch resistance.

  In the present invention, the resin layer may be a foaming agent-containing resin layer. In this case, the obtained laminated sheet means a so-called original fabric having a foaming agent-containing resin layer. And the foaming lamination sheet of this invention is obtained by making a foaming agent containing resin layer foam.

  As the resin composition for forming the foaming agent-containing resin layer, for example, a resin composition containing the above resin component, inorganic filler, pigment, pyrolytic foaming agent, foaming aid, crosslinking aid and the like can be suitably used. . In addition, stabilizers, lubricants and the like can be used as additives.

  Examples of the thermally decomposable foaming agent include azo series such as azodicarbonamide (ADCA) and azobisformamide; hydrazide series such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide. The content of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of the expansion ratio, it is 7 times or more, preferably about 7 to 10 times, and the pyrolytic foaming agent is preferably about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component.

  The foaming aid is preferably a metal oxide and / or a fatty acid metal salt. For example, zinc stearate, calcium stearate, magnesium stearate, zinc octylate, calcium octylate, magnesium octylate, zinc laurate, calcium laurate, laurin Magnesium acid, zinc oxide, magnesium oxide and the like can be used. About 0.3-10 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of these foaming adjuvants, about 1-5 mass parts is more preferable.

  When these foaming aids are used in combination with EMAA and ADCA foaming agents, the effect of the foaming aid is impaired by the reaction between the acrylic acid part of EMAA and the metallic foaming aid in the foaming process. There is a problem. Therefore, when EMAA and ADCA foaming agent are used in combination, it is preferable to use a carboxylic acid hydrazide compound as a foaming aid as described in JP-A-2009-197219. At this time, the carboxylic acid hydrazide compound is preferably used in an amount of about 0.2 to 1 part by mass with respect to 1 part by mass of the ADCA foaming agent.

  Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including the inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, an effect of suppressing heat generation during combustion, and the like are obtained. The content of the inorganic filler is preferably about 0 to 100 parts by mass and more preferably about 20 to 70 parts by mass with respect to 100 parts by mass of the resin component.

  For pigments, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve) ), Cadmium red, ultramarine, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide. Examples of organic pigments include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone. Perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine). The content of the pigment is preferably about 10 to 50 parts by mass, more preferably about 15 to 30 parts by mass with respect to 100 parts by mass of the resin component.

  In the present invention, the foaming agent-containing resin layer may be resin-crosslinked by electron beam irradiation. What is necessary is just to implement according to the method described in the postscript manufacturing method as a method of irradiating an electron beam to a foaming agent containing resin layer, and the method of making it foam. The thickness of the foaming agent (including the foaming agent-containing resin layer) is preferably about 40 to 100 μm, and the thickness of the foamed resin layer after foaming in the case of the foaming agent-containing resin layer is about 300 to 700 μm. preferable.

Non-foamed resin layers A and B
The foaming agent-containing resin layer may have a non-foamed resin layer on one side or both sides.

  For example, the back surface (surface on which the base material is laminated) of the foaming agent-containing resin layer may have a non-foamed resin layer B (adhesive resin layer) for the purpose of improving the adhesive force with the base material.

  The resin component of the adhesive resin layer is not particularly limited, but an ethylene-vinyl acetate copolymer (EVA) is preferable. As the EVA, a known or commercially available EVA can be used. In particular, the vinyl acetate component (VA component) is preferably 10 to 46% by mass, more preferably 15 to 41% by mass.

  The thickness of the adhesive resin layer is not limited, but is preferably about 5 to 50 μm.

  The upper surface of the foaming agent-containing resin layer is mainly non-foamed to protect the foaming agent-containing resin layer and to prevent the function of the adsorbent from deteriorating due to volatile components such as gas generated during the foaming agent-containing resin layer foaming process. The resin layer A may be formed.

  Examples of the resin component of the non-foamed resin layer A include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, and fluorine resins. Of these, polyolefin resins are preferred.

  Examples of polyolefin resins include polyethylene (low density polyethylene (LDPE) or high density polyethylene (HDPE)), polypropylene, polybutene, polybutadiene, polyisoprene, and other resins, and ethylene and α-olefins having 4 or more carbon atoms. Polymers (linear low density polyethylene (LLDPE)), ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer and other ethylene ( Examples include at least one of a (meth) acrylic acid copolymer, an ethylene-vinyl acetate copolymer (EVA), a saponified ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, and an ionomer. In the present invention, in particular, when a vinyl chloride resin is used as the resin in the resin layer, the non-foamed resin layer A (especially ethylene-vinyl alcohol co-polymer) is used to suppress the durability of the laminated sheet and the deterioration of the function of the adsorbent. It is preferable to form a polymer layer). In addition, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and the same applies to the portions described as other (meth).

  The thickness of the non-foamed resin layer A is not limited, but is preferably about 2 to 50 μm.

  In the present invention, also from the viewpoint of production described later, when the foaming agent-containing resin layer is provided, an embodiment in which the non-foaming resin layer B, the foaming agent-containing resin layer, and the non-foaming resin layer A are formed in order is preferable. The non-foamed resin layer B and / or the non-foamed resin layer A may be formed by extrusion film formation, or may be formed by heat laminating each film.

Pattern Pattern Layer In the laminated sheet of the present invention, a pattern pattern layer may be formed on the base material, the foaming agent-containing resin layer, the non-foamed resin layer A or each coating layer as necessary.

  The pattern layer imparts design properties to the laminated sheet and the foamed laminated sheet. Examples of design patterns include wood grain patterns, stone patterns, grain patterns, tiled patterns, brickwork patterns, fabric patterns, leather patterns, geometric figures, characters, symbols, abstract patterns, etc. Can be selected.

  The pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, offset printing, and the like. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent can be used. These inks may be known or commercially available.

  As the colorant, for example, a pigment used in the above-described foaming agent-containing resin layer can be appropriately used.

  The binder resin can be set according to the type of the base sheet. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy Resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Chlorinated organic solvents; and water. These solvents (or dispersion media) can be used alone or in the form of a mixture.

  The thickness of the design pattern layer is different from the type of design pattern, but is generally preferably about 0.1 to 10 μm.

Primer layer substrate, resin layer, on the non-foamed resin layer A or the design pattern layer, a primer layer may be formed as needed.

  As the resin contained in the primer layer, for example, acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene, and the like can be used. Particularly, acrylic, chlorinated polypropylene, etc. Is desirable.

  Examples of the acrylic include, for example, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, and (meth) acrylate methyl- (meth) acrylic acid. (Meth) such as butyl copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer An acrylic resin made of a homopolymer or a copolymer containing an acrylate ester may be mentioned.

  Polyurethane is a composition having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent).

  As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.

  As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate ) Isocyanates are used.

The thickness of the primer layer is not limited, but is preferably about 0.1 to 10 μm, more preferably about 0.1 to 5 μm.
≪Foamed laminated sheet≫
The foamed laminated sheet of the present invention can be obtained by foaming the foaming agent-containing resin layer of the laminated sheet. The heating conditions at the time of foaming are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds.

  The foamed laminated sheet of the present invention may be embossed from the top surface layer.

Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline, and a multiline groove.
≪Laminated sheet and foamed laminated sheet manufacturing method≫
As a manufacturing method of a lamination sheet and a foaming lamination sheet, for example, after forming a picture pattern layer on a base material and a foaming agent content resin layer, after forming a lower covering layer and an upper covering layer, and producing a lamination sheet, A foamed laminated sheet can be produced by heat-treating the foaming agent-containing resin layer into a foamed resin layer.

  When the foaming agent-containing resin layer has a non-foamed resin layer on one side or both sides, simultaneous extrusion film formation by a T-die extruder is suitable. For example, in the case of having non-foamed resin layers on both sides, a multi-manifold type T die capable of simultaneously forming three layers by simultaneously extruding molten resins corresponding to the three layers can be used.

  In addition, when an inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer and the foaming agent-containing resin layer is formed by extrusion film formation, an extrusion port (so-called die) of the extruder is used. Inorganic filler residues (so-called eyes and eyes) are easily generated, and this tends to be a foreign matter on the surface of the foaming agent-containing resin layer. Therefore, when an inorganic filler is included in the resin composition forming the foaming agent-containing resin layer, it is preferable to form a three-layer coextrusion film as described above. That is, it is possible to suppress the occurrence of the above-mentioned corners by co-extrusion film formation in a mode in which the foaming agent-containing resin layer is sandwiched between non-foamed resin layers.

  After forming the foaming agent-containing resin layer, electron beam irradiation may be performed. Thereby, the resin component can be cross-linked to adjust the surface strength, foaming characteristics, etc. of the foamed resin layer. The energy of the electron beam is preferably about 150 to 250 kV, more preferably about 175 to 200 kV. The irradiation amount is preferably about 10 to 100 kGy, and more preferably about 10 to 50 kGy. A known electron beam irradiation apparatus can be used as the electron beam source.

  On the foaming agent-containing resin layer, if necessary, a pattern layer and a primer layer are formed in an arbitrary order, and then a lower coating layer and an upper coating layer are formed to form a laminated sheet, and then heat-treated and foamed. A foamed laminated sheet can be produced by making the agent-containing resin layer into a foamed resin layer. Each of these layers can be laminated by combining coating such as printing and coating, extrusion film formation and the like, and coating such as printing and coating can be performed according to a conventional method.

  The heat treatment conditions may be any conditions as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds.

  In the laminated sheet of the present invention, at least two layers of a lower coating layer and an upper coating layer are formed on a base material, and the lower coating layer contains a resin component and an organic-inorganic composite adsorbent, thereby being resistant to contamination. And chemical resistance is improved. In addition, since the total thickness of the lower coating layer and the upper coating layer is 15 μm or less, even if the lower coating layer containing the organic-inorganic composite adsorbent is not located on the outermost surface, it exhibits an excellent deodorizing function. In addition, problems such as blocking are avoided due to excellent drying properties, and productivity is high. These effects are also the same in the foamed laminated sheet obtained by foaming the foaming agent-containing resin layer.

It is a schematic diagram which shows an example of the layer structure of the lamination sheet of this invention.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
Using a known T-die extruder, films were formed in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B so that each layer had a thickness of 15 μm / 100 μm / 10 μm. The resulting laminate was obtained. The resin or resin composition used for forming each layer is as follows.
(A) Resin used for non-foamed resin layer A:
-LDPE "Petrocene 202, manufactured by Tosoh", 100 parts by mass (b) Resin used for non-foamed resin layer B:
-Ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Smitate CV5053), 100 parts by mass (c) Resin composition used for foaming agent-containing resin layer:
・ LDPE “Petrocene 202, manufactured by Tosoh”, 100 parts by mass ・ Foaming agent (manufactured by Eiwa Kasei Kogyo Co., Ltd., trade name: VINYHALL ACO3), 5 parts by mass ・ Calcium carbonate (Shiraishi Kogyo Co., Ltd., trade name: White) H), 30 parts by mass Titanium dioxide (pigment) (manufactured by DuPont Co., Ltd., trade name: Taipure R-108), 20 parts by mass Foaming aid (manufactured by ADEKA, trade name: ADK STAB OF-101 ), 5 parts by mass-Cross-linking agent (manufactured by JSR Corporation, trade name: Obster JVA-702), 1 part by mass Next, a backing paper (rice A weighing of 60 g / m ² , manufactured by Kojin Co., Ltd., WK-FKKD) was laminated. Next, the laminate was irradiated with an electron beam (200 kV, 30 kGy) from the non-foamed resin layer A side, and the foaming agent-containing resin layer was particularly resin-crosslinked. Next, by gravure printing, a pattern is formed by printing a texture pattern on the non-foamed resin layer A surface using a water-based ink (Daiichi Seika Kogyo Co., Ltd., trade name: Hydrick). A coating liquid A having the following composition is applied at a coating amount of 2.0 g / m ² to form a lower coating layer, and a coating liquid B having the following composition is further applied at a coating amount of 2.0 g / m ^2. Thus, an upper coating layer was formed (total thickness of both layers: 4 μm). This obtained the lamination sheet. The content of the organic-inorganic composite adsorbent in the lower coating layer (solid content) is 28.6% by mass.
(Coating fluid A)
・ Acrylic resin emulsion (solid content): 25 parts by mass ・ Organic inorganic composite adsorbent (manufactured by Toagosei Co., Ltd., product number: NS-231, average particle size: 4 μm) (solid content): 10 parts by mass ・ Water: 65 parts by mass (Coating fluid B)
・ Acrylic resin emulsion (solid content): 20 parts by mass ・ Spherical silicone rubber beads (Toray / Dow Coating / Silicone Co., product number: 33Additive) (solid content): 4 parts by mass ・ Silicone resin emulsion (solid content) ): 3 parts by mass Water: 73 parts by mass Then, in a heating exothermic furnace at 230 ° C., the foaming agent-containing resin layer is foamed to form a foamed resin layer, which is then passed between a cooling roll and a pressure roll, and embossed. A foamed laminated sheet having a concavo-convex pattern on the surface was produced by thermocompression bonding while molding.

Example 2
A foamed laminated sheet was obtained in the same manner as in Example 1 except that the spherical silicone beads of the upper coating layer were changed to 20 parts by mass of an inorganic adsorbent (manufactured by Sinanen Zeomic, product name: Zeomic, average particle size: 3 μm). The content of the inorganic adsorbent in the upper coating layer (solid content) is 46.5% by mass.

Example 3
A foamed laminated sheet was obtained in the same manner as in Example 2 except that the content of the organic-inorganic composite adsorbent in the lower coating layer was 3 parts by mass. The content of the inorganic adsorbent in the lower coating layer (solid content) is 10.7% by mass.

Example 4
A foamed laminated sheet was obtained in the same manner as in Example 2 except that the content of the inorganic adsorbent in the upper coating layer was 10 parts by mass. The content of the inorganic adsorbent in the upper coating layer (solid content) is 30.3% by mass.

Example 5
Foaming was performed in the same manner as in Example 2 except that the coating amount of the upper coating layer was 5.0 g / m ² , the coating amount of the lower coating layer was 5.0 g / m ^2, and the total thickness of both layers was 10 μm. A laminated sheet was obtained.

Example 6
Foaming in the same manner as in Example 2 except that the coating amount of the upper coating layer was 5.0 g / m ² , the coating amount of the lower coating layer was 10.0 g / m ^2, and the total thickness of both layers was 15 μm. A laminated sheet was obtained.

Example 7
Foaming as in Example 2 except that the coating amount of the upper coating layer was 10.0 g / m ² , the coating amount of the lower coating layer was 5.0 g / m ² and the total thickness of both layers was 15 μm. A laminated sheet was obtained.

Example 8
A foaming agent-containing resin layer having the following composition was laminated on a backing paper (rice weighed 60 g / m ² , WK-FKKD, manufactured by Kojin Co., Ltd.) so as to have a thickness of 100 μm.
(Resin composition used for foaming agent-containing resin layer)
・ Vinyl chloride resin (product name: R-720, manufactured by Tosoh Corporation): 100 parts by weight
・ Titanium dioxide (pigment made by DuPont, trade name: Taipure R-108): 17 parts by weight
・ Calcium carbonate: manufactured by Shiroishi Kogyo, trade name: Whiten H): 100 parts by weight
・ Plasticizer (Sanken processing, DOP): 55 parts by weight
・ Foaming agent (product name: ADCA # 3, manufactured by Eiwa Kasei): 4 parts by weight
-Foaming aid (made by ADEKA Co., Ltd., trade name: OF-101): 1 part by weight-Cell modifier (trade name: KF-110A-6): 1 part by weight Next, by gravure printing, A pattern layer is formed by printing a texture pattern on a foaming agent-containing resin layer using water-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Hydrick), and coating with the following composition on the pattern layer Liquid A is applied at a coating amount of 2.0 g / m ² to form a lower coating layer, and coating liquid C having the following composition is applied at a coating amount of 2.0 g / m ² to form an upper coating layer. (Total thickness of both layers: 4 μm). This obtained the lamination sheet. The content of the organic-inorganic composite adsorbent in the lower coating layer (solid content) is 40.0% by mass. The content of the inorganic adsorbent in the upper coating layer (solid content) is 46.5% by mass.
(Coating fluid A)
・ Acrylic resin emulsion (solid content): 25 parts by mass ・ Organic inorganic composite adsorbent (manufactured by Toagosei Co., Ltd., product number: NS-231, average particle size: 4 μm) (solid content): 10 parts by mass ・ Water: 65 parts by mass (Coating fluid C)
・ Acrylic resin emulsion (solid content): 20 parts by mass ・ Inorganic adsorbent (manufactured by Sinanen Zeomic, product name: Zeomic, average particle size: 3 μm) (solid content): 20 parts by mass ・ Silicone resin emulsion (solid content): 3 Mass parts ・ Water: 57 parts by mass Then, in a heating exothermic furnace at 230 ° C., after foaming the foaming agent-containing resin layer to form a foamed resin layer, it is passed between a cooling roll and a pressure roll, and embossed. Then, a foamed laminated sheet having a concavo-convex pattern on the surface was produced by thermocompression.

Example 9
A foaming agent-containing resin layer having the following composition was laminated on a backing paper (rice weighed 60 g / m ² , WK-FKKD, manufactured by Kojin Co., Ltd.) so as to have a thickness of 100 μm.
(Resin composition used for foaming agent-containing resin layer)
・ Vinyl chloride resin (product name: R-720, manufactured by Tosoh Corporation): 100 parts by weight
・ Titanium dioxide (pigment made by DuPont, trade name: Taipure R-108): 17 parts by weight
・ Calcium carbonate: manufactured by Shiroishi Kogyo, trade name: Whiten H): 100 parts by weight
・ Plasticizer (Sanken processing, DOP): 55 parts by weight
・ Foaming agent (product name: ADCA # 3, manufactured by Eiwa Kasei): 4 parts by weight
-Foaming aid (made by ADEKA Co., Ltd., trade name: OF-101): 1 part by weight-Cell modifier (trade name: KF-110A-6): 1 part by weight Next, by gravure printing, A texture pattern was printed on the laminate using a water-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Hydrick) to form a pattern layer, and a laminate B was obtained.

On the other hand, an ethylene-vinyl alcohol copolymer resin (manufactured by Kuraray Co., Ltd., trade name: EVAL FILM HF-ME, thickness: 12 μm, ethylene content: 44 mol%) pre-coated with an adhesive as a film layer, A lower coating layer is formed by applying the coating liquid A at a coating amount of 2.0 g / m ² on the upper surface (the side where the adhesive is not applied) of the film layer, and the coating is applied on the lower coating layer. Liquid C was applied at a coating amount of 2.0 g / m ² to form an upper coating layer to obtain a laminate C (total thickness of both layers: 4 μm). The content of the organic-inorganic composite adsorbent in the lower coating layer (solid content) is 40.0% by mass. The content of the inorganic adsorbent in the upper coating layer (solid content) is 46.5% by mass.
(Coating fluid A)
・ Acrylic resin emulsion (solid content): 25 parts by mass ・ Organic inorganic composite adsorbent (manufactured by Toagosei Co., Ltd., product number: NS-231, average particle size: 4 μm) (solid content): 10 parts by mass ・ Water: 65 parts by mass (Coating fluid C)
・ Acrylic resin emulsion (solid content): 20 parts by mass ・ Inorganic adsorbent (manufactured by Sinanen Zeomic, product name: Zeomic, average particle size: 3 μm) (solid content): 20 parts by mass ・ Silicone resin emulsion (solid content): 3 Part by mass: Water: 57 parts by mass By heating the above laminate B at 230 ° C. using a heating foaming furnace, the foaming agent-containing resin layer is foamed to form a foamed resin layer to obtain a laminate D. After that, the laminate D is passed between the cooling roll and the pressure roll on which the embossing mold is formed simultaneously with the above-described laminate C, and is subjected to thermocompression bonding while embossing, so that the foam lamination having a concavo-convex pattern on the surface A sheet was obtained.
Example 10
The content of the organic-inorganic composite adsorbent in the lower coating layer is 100 parts by mass, the coating amount is 5.0 g / m ² , the coating amount of the upper coating layer is 2.0 g / m ^2, and the total thickness of both layers is A foamed laminated sheet was obtained in the same manner as in Example 1 except that the thickness was 7 μm. The content of the organic / inorganic composite adsorbent in the lower coating layer (solid content) is 50% by mass.

Comparative Example 1
The organic-inorganic composite adsorbent of the lower coating layer is 20 parts by mass of the inorganic adsorbent (made by Sinanen Zeomic, trade name: Zeomic, average particle size: 3 μm), and the organic-inorganic composite adsorbent (manufactured by Toagosei Co., Ltd.) (Product number: NS-231, average particle size: 4 μm) A foamed laminated sheet was obtained in the same manner as in Example 2 except that the content was 10 parts by mass. The content of the inorganic adsorbent in the lower coating layer (solid content) is 44.4% by mass. The content of the organic-inorganic composite adsorbent in the upper coating layer (solid content) is 30.3% by mass.

Comparative Example 2
A foamed laminated sheet was obtained in the same manner as in Example 2 except that the organic-inorganic composite adsorbent of the lower coating layer was changed to 0 part by mass. The content of the inorganic adsorbent in the upper coating layer (solid content) is 46.5% by mass.

Comparative Example 3
A foamed laminated sheet was obtained in the same manner as in Example 1 except that the organic-inorganic composite adsorbent of the lower coating layer was changed to 0 part by mass.

Comparative Example 4
Foaming in the same manner as in Example 2 except that the coating amount of the upper coating layer was 7.0 g / m ² , the coating amount of the lower coating layer was 13.0 g / m ^2, and the total thickness of both layers was 20 μm. A laminated sheet was obtained. The content of the organic-inorganic composite adsorbent in the lower coating layer (solid content) is 28.6% by mass. The content of the inorganic adsorbent in the upper coating layer (solid content) is 46.5% by mass.

Comparative Example 5
Foaming in the same manner as in Example 2 except that the coating amount of the upper coating layer was 15.0 g / m ² , the coating amount of the lower coating layer was 5.0 g / m ^2, and the total thickness of both layers was 20 μm. A laminated sheet was obtained. The content of the organic-inorganic composite adsorbent in the lower coating layer (solid content) is 28.6% by mass. The content of the inorganic adsorbent in the upper coating layer (solid content) is 46.5% by mass.

Test example 1
For the foamed laminated sheets obtained in the examples and comparative examples, 1) ammonia deodorization performance, 2) aldehyde deodorization performance, 3) stain resistance, 4) chemical resistance, 5) embossability and 6) drying properties (production) Sex). Each test method and evaluation criteria are as follows.
≪Ammonia deodorization performance≫
A test piece (10 cm × 6 cm) was inserted into a Tedlar bag having an internal volume of 5 liters (L). A gas with an ammonia concentration of 250 ppm was prepared using a 28% aqueous ammonia solution and synthetic air ((nitrogen: oxygen) volume ratio: 4/1, RH 50%), and 3 liters (L) was fed into the Tedlar bag. The ammonia concentration immediately after gas injection and after storage for 6 hours in the dark was measured with a detector tube, and the ammonia removal rate (%) after 6 hours was calculated by the following formula.

Removal rate (%) = [{(initial concentration) − (concentration after 6 hours)} / (initial concentration)] × 100
The case where the removal rate was 100 to 60% was “A”, the case where it was 59 to 30% was “B”, and the case where it was 29% or less was “C”.
≪Acetaldehyde deodorization performance≫
A test piece (10 cm × 10 cm) was inserted into a 5 liter (L) Tedlar bag. Using a 99.5% acetaldehyde solution and synthetic air ((nitrogen: oxygen) volume ratio: 4/1, RH 50%), a gas with an acetaldehyde concentration of 60 ppm was prepared, and 1 liter (L) was fed into the Tedlar bag. The concentration of acetaldehyde immediately after gas injection and after storage for 24 hours in the dark was measured with a detector tube, and the acetaldehyde removal rate (%) after 24 hours was calculated by the following formula.

Removal rate (%) = [{(initial concentration) − (concentration after 24 hours)} / (initial concentration)] × 100
The case where the removal rate was 100 to 70% was “A”, the case where it was 69 to 40% was “B”, and the case where it was 39% or less was “C”.
≪Stain resistance≫
Contaminants (neutral detergent, soy sauce, coffee, crayon, aqueous pen) were each dropped on gauze placed on the sample, or a straight line was drawn, and after 24 hours, wiped with water and neutral detergent. As a result of visual evaluation, “C” was given when there were 2 or more types of dirt remaining after wiping, “B” was given when 1 type of dirt remained, and “A” when all could be wiped off.
≪Chemical resistance≫
A chemical (5% hydrochloric acid aqueous solution, 5% sodium hydroxide aqueous solution) was dropped onto each gauze placed on the sample and wiped off with water after 2 hours. As a result of visual evaluation, “C” was indicated when there was a mark remaining, “B” when a slight mark was left but there was no problem in use, and “A” when no mark was left.
≪Embossing aptitude≫
The embossability at the time of production of the foamed laminated sheet was determined by measuring the embossed plate unevenness depth and the formed unevenness depth to determine the forming rate. “Aging rate of 60% or more” was evaluated as “A”, “60-50%” as “B”, “50-40%” as “C”, and “less than 40%” as “D”.

The evaluation results of each test are shown in Table 1 below.
≪Dryness (Productivity) ≫
Two foamed laminated sheets immediately after production were superposed and left at 25 ° C. for a week with a load of ² kg / cm ² . When the foam laminate sheet is peeled off after one week, the resin of the upper coating layer of the lower foam laminate sheet is removed on the base material of the foam laminate sheet (blocking is recognized) as “B”, The case where the blocking was not observed was designated as “A”. If the dryness (productivity) of the foamed laminated sheet is good, the blocking is not recognized.

1. Base material
2. Non-foamed resin layer B
3. Foaming agent-containing resin layer
4. Non-foamed resin layer A
5. Pattern pattern layer
6. Lower coating layer
7. Upper coating layer

Claims (8)

A foam laminated sheet in which at least two layers of a lower coating layer and an upper coating layer are formed on a substrate,
(1) The lower coating layer contains an organic-inorganic composite adsorbent that adsorbs a resin component and a volatile compound, the resin component contains an acrylic resin,
(2) The upper coating layer contains a resin component, the resin component contains an acrylic resin,
(3) the total thickness of said lower cover layer and the upper coating layer Ri der less 15 [mu] m,
(4) having a foamed resin layer between the base material and the lower coating layer;
(5) Embossed from the top surface layer.
A foamed laminated sheet characterized by that. 2. The foamed laminated sheet according to claim 1 , wherein the foamed resin layer is an olefin resin layer. The upper covering layer contains an inorganic adsorbent for adsorbing the volatilization compounds, foamed laminate sheet according to claim 1 or 2. The foamed laminated sheet according to any one of claims 1 to 3 , wherein a total thickness of the lower coating layer and the upper coating layer is 10 µm or less. The foamed laminated sheet according to any one of claims 1 to 4, wherein the foamed resin layer has a non-foamed resin layer on one side or both sides. The foamed laminated sheet according to any one of claims 1 to 5 , wherein the lower coating layer contains an organic-inorganic composite adsorbent that adsorbs 5 to 80 parts by mass of the volatile compound with respect to 100 parts by mass of a resin component. . The foamed laminated sheet according to any one of claims 3 to 6 , wherein the upper coating layer contains an inorganic adsorbent that adsorbs 5 to 120 parts by mass of the volatile compound with respect to 100 parts by mass of the resin component. The foamed laminated sheet according to any one of claims 1 to 7 , wherein the foamed resin layer is resin-crosslinked by electron beam irradiation.

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